CN1122004C - Halogen exchange reactions and uses thereof - Google Patents

Abstract

A mixture of (i) finely-divided alkali metal fluoride (e.g., KF), (ii) haloaromatic compound having at least one halogen atom of atomic number greater than 9 on an aromatic ring (e.g., C6Cl6), and (iii) an aminophosphonium catalyst (e.g., Et2N)4PBr), is heated at a temperature at which fluorine replaces one or more of the ring halogen atom of the haloaromatic compound. Processes are described wherein fluorinated perhalobenzenes such as C6ClF5 and C6BrF5 formed in this manner are converted efficiently and at low cost to a variety of industrially important products.

Description

Halogen exchange reaction and its application

technical field

This invention relates to halogen exchange reactions involving halogenated aromatic compounds and alkali metal fluorides, and in particular to an improved process for the preparation of polyfluorinated aromatic compounds by catalyzed halogen exchange reactions, and to the industrial importance of this process technology application.

Background of the invention

The halogen exchange reaction of fluorinated halogenated aromatic compounds with alkali metal fluorides has been extensively studied so far. Typical studies include the reaction of chlorinated aromatic compounds with potassium fluoride, rubidium fluoride, or cesium fluoride by heating the reactants to very high temperatures (greater than 400°C) in the absence of auxiliary diluents or solvents. or in an aprotic solvent such as sulfolane at a temperature of about 200-230°C. Organic fluorine compounds such as pentafluoro compounds are formed by reacting corresponding chlorine or bromine substituted compounds with alkali metal halides such as potassium fluoride in a benzonitrile solvent at 190-400°C in a sealed autoclave under autogenous pressure Studies on benzonitrile, tetrafluorophthalonitrile, and pentafluoropyridine have also been reported.

The use of catalysts in some exchange reactions has also been investigated. These catalysts include quaternary ammonium salts, metal carbonyls, crown ethers and cryptates.

Halogen exchange reactions are in most cases slow and tend to form mixed products in which the yield of polyfluorinated aromatics is relatively low, especially if the halogenated aromatics used are This is especially the case with polyhalogenated aromatic compounds such as nitro or carbonyl groups. For example, when hexachlorobenzene is reacted with potassium fluoride, the typical product mixture is a multi-product mixture containing hexafluorobenzene and various chlorofluorobenzenes.

Therefore, there is a need for a simple industrial method, so that the halogen exchange reaction widely used in various halogenated aromatic compounds can be carried out in a large-scale reaction device under relatively mild reaction conditions and the target product can be obtained. Commercially acceptable Yield. In addition, the provision of a method that can produce fluorinated perhalogenated aromatic compounds such as monochloropentafluorobenzene, bromopentafluorobenzene and hexafluorobenzene on a large scale and in high yield under relatively mild reaction conditions will be particularly helpful to the art Contributions are welcome.

The present invention is believed to most effectively meet these needs. In addition, the present invention will enable more efficient, low-cost production of a variety of important industrial end products.

Brief description of the invention

The invention provides a novel catalytic halogen exchange reaction using alkali metal fluoride as a fluorine source. This method can produce a variety of fluorinated aromatic compounds under relatively mild reaction conditions. In addition, the method can use halogenated aromatic compounds containing one or more halogen atoms other than fluorine as starting materials, including compounds without active groups and compounds with one or more active groups in the molecule. In fact, the method is particularly suitable for perhalogenated aromatic compounds without active groups in the molecule, such as hexachlorobenzene, hexabromobenzene, pentachlorofluorobenzene, tetrachlorodifluorobenzene, trichlorotrifluorobenzene and polyfluorination of dichlorotetrafluorobenzene. In addition, the catalytic process can be performed with less excess alkali metal than conventionally required by prior art processes.

The significant advance made possible by the present invention is at least in part due to the use of an aminophosphonium catalyst in the process. As an example of these advances, comparative studies on a 50 liter scale showed that in the reaction of hexachlorobenzene and potassium fluoride to form chloropentafluorobenzene and hexafluorobenzene, the aminophosphonium catalyst according to the invention included four The use of (diethylamino)phosphonium bromide resulted in the following improvements in yield:

a) The output of the target product based on the amount of raw material input increased by 12%-25%.

b) The yield of the target product based on the input amount of hexachlorobenzene is increased by 35%-95%.

c) The molar yield of the target product is increased by 49%-86%.

Accordingly, in accordance with one embodiment of the present invention there is provided a halogen exchange process which comprises heating at one or more reaction temperatures a stirred medium containing (i) at least one finely divided alkali metal fluoride, ( ii) a mixture of at least one halogenated aromatic compound having an aromatic ring and at least one halogen atom having an atomic number greater than 9, and (iii) a component of an aminophosphonium catalyst such that the halogenated aromatic compound At least one of said halogen atoms of the group of compounds is replaced by a fluorine atom.

In a preferred embodiment of the invention said (i) at least one finely divided alkali metal fluoride is predominantly or exclusively potassium fluoride.

In a preferred embodiment of the present invention, the method is carried out using at least one halogenated aromatic compound that does not contain any reactive functional groups on the aromatic ring as a starting halogenated aromatic compound for halogen exchange , a halogen atom with an atomic number greater than 9 is bonded to its aromatic ring.

A particularly preferred embodiment involves the halogen exchange process using a starting halogenated aromatic component which is one or more halogenated aromatic compounds on the aromatic rings of which not only It does not contain any active functional groups, and does not contain hydrogen atoms, and the halogen atoms with atomic number greater than 9 are bonded to its aromatic ring. Particularly preferred _such haloaromatic compounds are perhaloaromatic compounds of _the formula _C6ClnBrmFp , wherein n is 0-6, m _is 0-6, p is 0-5, and n , the total number of m and p is 6. Compounds in which m is 0 have been used with particular success.

In another preferred embodiment, the mixture in the process of the invention is a predominantly solids mixture at least prior to heating.

Another preferred embodiment comprises carrying out the process of the invention such that the substantially anhydrous agitated mixture is, when heated to one or more temperatures, a mixture of solids dispersed in a continuous liquid phase. The operation of these continuous liquid phases comprising at least one non-halogen, polar, anhydrous or substantially anhydrous aprotic solvent constitutes an additional preferred embodiment of the invention.

In a more preferred embodiment of the present invention, said aprotic solvent is mainly or completely (a) benzonitrile, (b) at least one liquid alkyl benzonitrile, (c) nitrobenzene, (d) at least one liquid alkyl-nitrobenzene, or (e) a mixture of at least two of (a), (b), (c) and (d).

In another preferred embodiment of the present invention, a gas-phase mixture of perhalogenated benzenes is formed such that at least one relatively volatile perhalogenated benzene component is mixed with one or more of said gas-phase mixtures The less volatile perhalobenzene components are separated and recovered; and at least a portion of the one or more less volatile perhalobenzene components are recycled back to a current or future halogen exchange reaction.

A preferred catalyst component for use in various embodiments of the present invention is a tetrakis(dihydrocarbylamino)phosphonium halide.

These and other specific embodiments, features and advantages of the present invention will be further apparent from the ensuing description, drawings and claims.

Brief description of the drawings

Figure 1 schematically depicts a batch industrial plant for carrying out the process without the use of auxiliary solvents/diluents.

Further description of the invention

The basic raw material of the method of the present invention is one or more haloaromatic compounds containing one or more halogen atoms other than fluorine connected to the aromatic ring, one or more alkali metals other than lithium (preferably the atomic number is 19 or Alkali metal fluorides of the above alkali metals), and one or more aminophosphonium catalysts. The use of one or more auxiliary solvents or diluents is optional, but preferred. Halogenated aromatic compound components

Any aromatic compound having a substitutable halogen atom other than fluorine on the aromatic ring is a candidate component for this method. The compound may contain a carbocyclic aromatic nucleus (ie at least one benzene ring system) or a heteroaromatic ring system. The compound may also contain one or more reactive groups such as nitro, nitroso, carbonyl, cyano and sulfonic acid groups, or may be free of any of these groups. The compound contains one or more chlorine, bromine or iodine atoms or any combination of chlorine, bromine and/or iodine atoms on the aromatic ring, and may also contain One or more such halogen atoms bonded or fused to one or more non-aromatic carbocyclic or heterocyclic rings. In addition, the compound may contain one or more fluorine atoms at any position of the molecule including one or more fluorine atoms attached to the aromatic ring, forming at least one Compounds with aromatic rings of halogen atoms. The heteroatoms in the halogen-substituted, preferably fluorine-substituted, aromatic rings are 1-3 nitrogen atoms (for example, the compound is aromatic-halogenated pyridine, aromatic-halogenated pyridine, aromatic-halogenated pyridazine, aromatic-halogenated pyrimidine, aromatic ring halogenated pyrazine, aromatic ring halogenated triazine, wherein at least one halogen atom attached to the aromatic ring is not a fluorine atom; or the compound has at least these ring systems). Other heteroatoms that may be present in the side chains of the compound or in other ring systems include one or more nitrogen, oxygen, sulfur, phosphorus, boron or silicon atoms, or a combination of two or more of these atoms. Generally, the haloaromatic component may contain up to 50 carbon atoms in the molecule, preferably up to 20 carbon atoms in the molecule.

Halogenated aromatic compounds that do not contain any reactive groups in the molecule are preferred because they are generally less susceptible to halogen exchange reactions than their counterparts containing reactive functional groups in the molecule.

Among the carbocyclic and heterocyclic aromatic compounds, carbocyclic haloaromatic compounds are the preferred components. As stated above, a halogenated aromatic compound that does not contain any active groups on the aromatic ring bonded to a halogen atom with an atomic number greater than 9 and that does not contain any hydrogen atoms on the aromatic ring constitutes the halogenated aromatic compound of the present method Another preferred class of components or raw materials. Particularly preferred _such haloaromatic compounds are perhaloaromatic compounds of _the formula _C6ClnBrmFp , wherein n is 0-6, m _is 0-6, p is 0-5, and n , the total number of m and p is 6. Compounds where m is 0 are particularly desirable components because of their good reactivity in this process and are generally less expensive. Moreover, a method that is particularly urgently needed at present is to obtain polychlorinated analogues such as hexachlorobenzene, pentachlorofluorobenzene, tetrachlorodifluorobenzene, trichlorotrifluorobenzene, or dichlorotetrafluorobenzene, or any of them Polyfluorobenzenes, especially chloropentafluorobenzene and hexafluorobenzene, are efficiently produced in mixtures of two or more; this need has been met by the present invention.

The present invention can also meet the requirements from polybrominated analogues such as hexabromobenzene, pentabromofluorobenzene, tetrabromodifluorobenzene, tribromotrifluorobenzene, or dibromotetrafluorobenzene, or any two or more of them. The need for an efficient method of producing bromopentafluorobenzene in a mixture of

Other halogenated aromatic compounds useful in the present invention that can be converted to aromatic ring fluorinated compounds include, for example, mono-, di-, tri-, tetra-, and pentachlorobenzenes, their bromine and iodine analogs; mono- and polychlorinated, Brominated, iodinated naphthalene, tetrahydronaphthalene, acenaphthene, biphenyl and terphenyl; analogues of the foregoing substances substituted with alkyl and haloalkyl; diaryl ethers and monoalkyl substituted with chlorine, bromine and iodine Monoaryl ether; 2-chloronitrobenzene; 4-chloronitrobenzene; 2,4-dinitrochlorobenzene; 3,4-dichloronitrobenzene; 3-chloro-4-fluoronitrobenzene ; 2,4,6-trichloropyrimidine; tetrachloropyrimidine; 2-chlorobenzonitrile; 4-chlorobenzonitrile; pentachlorobenzonitrile; tetrachloroisophthalonitrile; 5-dichloropyridine; pentachloropyridine; 4-chlorophthalic anhydride; and other similar compounds, such as those mentioned in US Patent No. 4,684,734 by Keerda et al. Alkali Metal Fluoride Components

Potassium fluoride, rubidium fluoride and cesium fluoride are the preferred alkali metal halides used in the practice of this invention because of their higher reactivity in this exchange reaction. However, sodium fluoride can also be used, especially when the halogenated aromatic compound component has reactive functional groups on the halogenated aromatic ring, and only partial substitution of the aromatic ring chlorine, aromatic ring bromine or aromatic ring iodine is desired Even more so.

Any combination of two or more alkali metal fluorides may be used, including combinations when lithium fluoride is present. Therefore, mixtures of potassium fluoride, rubidium fluoride and/or cesium fluoride with sodium fluoride or lithium fluoride, or with both sodium fluoride and lithium fluoride, may also be used if desired, although this Not a recommended solution. In order to enhance their reactivity, the alkali metal fluoride should be in finely divided state or powder anhydrous form. Potassium fluoride is the preferred fluorinating reagent because it is the most cost-effective reagent. A traditional method of bringing the fluorinating reagent to a suitable anhydrous state is to slurry the fluoride salt in a suitable volatile hydrocarbon, such as benzene, which forms an azeotrope with water, and heat the mixture to dehydrate while properly controlling and handling the vapors.

A particularly useful form of potassium fluoride for use in the present method is prepared by the method described by TPSmyth, A. Carey and BK Hodnett in Tetrahedron, Volume 51, No. 22, pp. 6363-6376 (1995) Lively form of KF. Briefly, the method involved recrystallization of KF from methanol solution by slow evaporation of the solvent, followed by drying at 100 °C. Another useful form of potassium fluoride is KF dispersed on _CaF2 . This material is described by JH Clark, AJ Hyde and DK Smith in J. Chem. Soc. Chem. Commun, 1986, 791. Other reactive forms of KF can also be used, such as spray-dried KF (N. Ishikawa et al., Chem. Letts, 1981, 761) and freeze-dried KF (Y. Kimura et al., Tetrahedron Letters, 1989, 1271). It is also believed possible to employ one or more of the above activation methods with other alkali metal fluorides such as cesium fluoride and/or sodium fluoride.

In order to enhance its reactivity, the alkali metal fluoride charged into the reaction mixture is preferably in finely divided or powdered anhydrous or substantially anhydrous form, that is, its water content, if any, should not exceed 3000 Parts per million (ppm) by weight. Potassium fluoride is the preferred fluorinating agent because it is the most cost-effective agent and most preferably has a water content, if any, of less than 1000 ppm. The alkali metal fluoride particles should generally have an average surface area of at least 0.20 m ² /g. In this regard, the larger the average surface area of the alkali metal fluoride particles, the better. It is therefore preferred that the alkali metal fluoride particles initially have an average surface area of at least 0.40 m ² /g, more preferably at least 0.80 m ² /g. For example, the reaction rate of spray-dried potassium fluoride with a typical water content of 1000 ppm and an average surface area of 0.85 m ² /g was found to be 0.25 m ² /g average The surface area of the spray-dried KF was nearly four times that of the reaction rate.

The proportion of alkali metal fluoride relative to the halogenated aromatic compound component used can be varied. Theoretically, there is no upper limit for the amount of alkali metal fluoride used relative to the amount of haloaromatic compound used. If a very large excess of alkali metal fluoride is used relative to the amount of substitutable halogen present in the haloaromatic compound, the haloaromatic compound will be the limiting reagent and the excess alkali metal fluoride will remain in large quantities. The use of an appropriate excess of alkali metal fluoride can be beneficial in the sense that when the reaction is carried out without an auxiliary diluent, excess alkali metal fluoride can serve to facilitate stirring or other agitation of the reaction mixture. of. On the other hand, however, if the excess of alkali metal fluoride exceeds a certain level, it is not consistent with common sense and practice. Thus, the amount of alkali metal fluoride will generally not exceed 10 or 15 moles, and in most cases will be less than this, per mole of substitutable halogen in the starting haloaromatic component used. On the other hand, if the amount of substitutable halogen in the haloaromatic component used exceeds the molar amount of alkali metal fluoride used, the alkali metal fluoride will be the controlling agent. This factor should therefore be considered in most cases when selecting the ratios to be used in any given reaction. In general, the reactants are often used in proportions ranging from 0.8 to 5 moles of alkali metal fluoride per mole of substitutable halogen in the haloaromatic component used, and in some preferred cases such as using In the case of auxiliary diluents, the reactants are added in a ratio of 1 to 3 moles of alkali metal fluoride per mole of substitutable halogen in the halogenated aromatic compound component used. Aminophosphonium Catalyst Components

The essential catalyst component of the present invention is at least one aminophosphonium catalyst component. One or more other cocatalysts may also be included, if desired, so long as at least one aminophosphonium catalyst component is added to the reaction zone or reaction mixture simultaneously or in any order. The use of aminophosphonium catalysts rather than cocatalysts is presently believed to be preferred.

The aminophosphonium catalyst is preferably added in the form of a tetrakis(dihydrocarbylamino)phosphonium halide. This compound can be given the molecular formula

(R ₂ N) ₄ P ^ X ^

to represent, wherein R is a hydrocarbon group, preferably an alkyl group; X is a halogen atom, preferably a fluorine or bromine atom, most preferably a bromine atom. Examples of such aminophosphonium compounds are:

Tetra(diethylamino)phosphonium fluoride

Tetra(dibutylamino)phosphonium bromide

Tris(diethylamino)(dipropylamino)phosphonium iodide

Tetrakis(dibutylamino)phosphonium iodide

Tris(dibutylamino)(diethylamino)phosphonium iodide

Tris(dipropylamino)(diheptylamino)phosphonium iodide

Tetra(dipropylamino)phosphonium bromide

Tris(diethylamino)(dihexylamino)phosphonium iodide

Tris(diethylamino)(dibutylamino)phosphonium iodide

Tris(dipropylamino)(heptylpropylamino)phosphonium iodide

Tetrakis(dipropylamino)phosphonium iodide

Tris(dipropylamino)(ethylpropylamino)phosphonium iodide

Tetrakis(diethylamino)phosphonium iodide

Tetrakis(diethylamino)phosphonium bromide

Tetrakis(diphenylamino)phosphonium bromide

Tetrakis(di-m-tolylamino)phosphonium bromide

Tetrakis(dibenzylamino)phosphonium bromide

Tetrakis(dicyclohexylamino)phosphonium bromide

Tetra(dioctylamino)phosphonium bromide

Tetrakis(didecylamino)phosphonium bromide

Tetra(diethylamino)phosphonium chloride

Tetra(dipropylamino)phosphonium chloride

Tetra(dibutylamino)phosphonium chloride

Tetra(dihexylamino)phosphonium chloride

A preferred group of aminophosphonium catalysts charged to the reactor consists of chlorided and/or brominated tetrakis(dialkylamino)phosphoniums. Among these compounds, the aminophosphonium catalyst component is more preferably one or more tetrakis(dialkylamino)phosphonium bromides, wherein the alkyl groups can be the same or different, and each alkyl group has 12 or less carbon atoms . The most preferred compound in the present invention is tetrakis(diethylamino)phosphonium bromide. The preparation of these compounds can be found in Koidan, Marchenko, Kudryavtsev and Pinchuk, Zh. Obshch. Khim., 1982 , 52, 2001, the English translation of which is available from Plenum Publishing Company.

The method for preparing tetrakis(diethylamino)phosphonium bromide comprises the following four steps (where Et represents an ethyl group):

1)

2)

3)

4)

In this method, carbon tetrachloride and phosphorus trichloride are first charged into the reactor, and then diethylamine is slowly added at low temperature (up to 30°C). This will lead to the formation of the dichloromethylenephosphoramido intermediate. Ammonia (gas) is then added to the reactor to form the imidophosphorus hydrochloride intermediate. After stirring for a period of time, the contents of the reactor were filtered. The concentrated filtrate is then treated with sodium hydroxide solution to form the base-free iminoaminophosphorus compound. It was extracted with dichloromethane. The extract was dried over calcium chloride and the dichloromethane was distilled off. The solid product is mixed with sodium hydroxide and ethyl bromide and added to the reactor to give the tetrakis(diethylamino)phosphonium bromide product. The product was extracted with dichloromethane. The extract was dried and dichloromethane was evaporated. The crude product was then recrystallized from a mixture of dichloromethane and ether. The recrystallized, wet product is then dried.

Typical raw material additions in these continuous operations are as follows: 3985 grams (25.7 moles) of carbon tetrachloride, 270 grams (1.96 moles) of phosphorus trichloride, 880 grams (12.39 moles) of diethylamine, 40 grams (2.35 moles) of ammonia ), 315 grams of 50% sodium hydroxide, 472 grams of dichloromethane, 23.6 grams of calcium chloride (anhydrous), 534 grams of 20% sodium hydroxide, 230 grams of bromoethane (2.12 moles), 1643 grams of dichloromethane, Calcium chloride (anhydrous) 82.1 grams, dichloromethane 450 grams, ether 450 grams. Typical product yields are 300 grams (0.754 moles) per batch.

The aminophosphonium catalyst is used in a catalytically effective amount typically in the range of 3-6 mole percent, preferably 4-5 mole percent, based on the total amount (moles) of halogenated aromatic compounds also present in the reaction zone. Co-catalyst component

The tetrakis(dihydrocarbylamino)phosphonium halide catalysts are effective for direct addition as a single catalyst component or for indirect addition (ie, after mixing with one or more other components to be added to the reaction system). This mode of catalyst operation is preferred. As noted above, however, one or more co-catalyst components may also be used if desired.

One type of these promoter materials consists of one or more crown ethers or cryptates. These compounds, sometimes referred to as "cage compounds," can be helpful in further enhancing the reactivity of alkali metal fluorides. See US Patent No. 4,174,349 to Evans et al. in this regard. Full descriptions of crown ethers and cryptates can be found in the following documents: U.S. Patent 3,687,978 of Evans et al. and related references cited therein; Chem.Rev. of JJChristensen et al., 1974,74,351 ; Heterocycl.Chem., 1974 , 11, 649; Angew.Chem.Int.Ed.Engl. of CJPedersen et al., 1972 , 11, 16; PCR Technical Bulletin with the acronym KRYPTOFIX; and J.Org.Chem., 1977 , Vol42, No.10, 2A. The crown ether or cryptate is used in a catalytically effective amount, typically in the range of 0.01 to 1 mole of crown ether or cryptate per mole of halogenated aromatic compound in the reaction mixture.

Another usable cocatalyst consists of, (i) at least one polyvalent inorganic fluoride of boron, aluminum, tin, phosphorus, titanium, zirconium, hafnium, or silicon, or (ii) at least one such polyvalent inorganic Double salts of fluorides and alkali metal fluorides, or (iii) combinations of (i) and (ii) mentioned; the precondition is (i), (ii), and (iii) inorganic fluorides In a stable valence state such that (i), (ii), and (iii) have no oxidative properties where possible. Bennett et al reported in U.S. Patent No. 3,453,337 that in the non-catalyzed reaction of hexachlorobenzene and KF or NaF, the presence of the above-mentioned (i), (ii) and (iii) compounds can be used under milder reaction conditions Increased product yields with shorter reaction times. Examples of suitable multivalent compounds also include LiBF ₄ , NaBF ₄ , KBF ₄ , K ₂ SnF ₆ , KPF ₆ , K ₂ SiF ₆ , Na ₂ TiF ₆ , K ₂ TiF ₆ , Na ₂ ZrF ₆ , K ₂ ZrF ₆ , Na ₂ HfF ₆ , K ₂ HfF ₆ . These compounds may be used in catalytically effective amounts of up to 50% or more by weight of the alkali metal fluoride charged in the reaction mixture. Typical amounts range from 2 to 25% by weight of the alkali metal fluoride used.

Other co-catalysts that can be considered include quaternary ammonium salts, such as by J.Dockx's Synthesis, 1973, 441; C.M.Starks and C.Liotta's Phase Transfer Catalysis, 1978, Academic Press, New York; and W.P.Weber and G.W.Gokel's Examples described by PhaseTransfer Catalysis in Organic Synthesis, 1977, Springer-Verlag, Berlin-Heidelberg-New York; and metal carbonyls, e.g. by J.Am.Chem.Soc. by M.F.Semmelhack and H.T.Hall, 1974, 96, 7091 compounds described in .

Both the function and composition of the aminophosphonium catalyst and the aforementioned cocatalyst (if used) can vary. Functionally, they can be used to facilitate or enhance fluorination exchange reactions, for example (a) by increasing the reaction rate without affecting yield or selectivity, (b) by increasing yield or selectivity or both without affecting The reaction rate, or (c) is improved by increasing the reaction rate and improving the yield or selectivity or both. The term "catalyst" or "cocatalyst" as used herein therefore means a material used in such a way that it improves or enhances the reaction process in some way or other such that the inclusion or presence of the material or its derivatives in the reaction mixture produces At least one beneficial use effect has been achieved. The mechanism by which its effect is produced is not critical, so long as the advantages of its use outweigh the disadvantages, if any.

With regard to the composition of catalysts and cocatalysts, the composition of a material is defined herein as it would be before it is combined with any other materials used in the process. The composition of the catalyst may change after it has been added and/or mixed with one or more of the other components used in the process and/or as the reaction proceeds, and if so, whether supplemented or not and whether or not it will occur No matter how much it is changed, the final changed material will correspond to the function of the catalyst in whole or in part. operating conditions

The process may be carried out by dry mixing finely divided substantially anhydrous alkali metal fluoride, a halogenated aromatic compound containing at least one halogen atom with an atomic number greater than 9 in an aromatic ring, and an aminophosphonium catalyst in one or The mixture is heated at a reaction temperature such that at least one of the halogen atoms of the halogenated aromatic compound is replaced by a fluorine atom at the temperature. Alternatively, the aforementioned components may be heated to one or more of such reaction temperatures when mixed with an auxiliary solvent/diluent. The solvent or diluent used is preferably a polar aprotic solvent such as sulfolane (tetramethylenesulfone), N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfone , dimethyl sulfoxide, triglyme (triethylene glycol dimethyl ether), N-methylpyrrolidinedione, or benzonitrile, or a mixture of two or more of these materials, As well as similar polar aprotic solvents which are liquid at the chosen reaction temperature, more preferably such solvents which remain liquid at or below 10°C. Benzonitriles and liquid ring-substituted alkylbenzonitriles such as o- and m-methylbenzonitriles, especially benzonitriles themselves, are preferred solvents. Another preferred aprotic solvent is nitrobenzene because of its excellent solvency and relatively low cost. Other solvents/diluents useful in the process are halogenated aromatic compounds which are liquid at least at the reaction temperature employed, preferably below the reaction temperature. Examples thereof include hexafluorobenzene, octafluorotoluene, perfluorodecalin, dichlorotetrafluorobenzene, trichlorotrifluorobenzene, and tetrachlorodifluorobenzene. The latter three of these compounds are particularly desirable solvents/diluents because they function not only as solvents/diluents but also as good reactants in the preparation of chloropentafluorobenzene.

Whether or not the reaction mixture has a solvent/diluent, the reaction mixture should be sufficiently stirred during the reaction to allow intimate contact of the different starting materials in the mixture. The use of mechanical agitation equipment such as mechanical stirrers, rocking autoclaves or similar devices is therefore highly recommended.

The reaction temperature typically ranges from 150°C to 350°C, preferably from 170°C to 250°C. When the process is carried out in slurry form using a liquid aprotic solvent or diluent, it is preferably carried out at a temperature or temperatures in the range 200°C to 240°C. The reaction can be carried out at atmospheric, subatmospheric or superatmospheric pressures. In most cases it is desirable and convenient to carry out the reaction under autogenous pressure in a closed system. The reaction time typically ranges from 2 to 48 hours, preferably from 5 to 20 hours. It will be appreciated based on this disclosure that deviations from any of the ratio ranges and/or reaction conditions set forth above may be made if such deviations are necessary or desirable.

Examples 1-12 below describe the halogen exchange process of the present invention carried out without auxiliary solvents or diluents. These examples and all examples that follow are illustrative of the invention, not limiting.

Examples 1-12

Adopt the equipment of the type shown in Fig. 1, this equipment comprises a stainless steel reactor (316S) 10, bottom outlet valve 12, vapor condenser 14, bottom discharge valve 12, the capacity of 50 liters and equipped with an electric heating system (not shown). Receiver 16, vacuum system 18, a pressure relief system (not shown) controlled by an auxiliary operating system, nitrogen inlet line 20 to break vacuum, pressure measurement/regulator 22, temperature measurement/regulator 24, and solids feed Entrance 26. The reactor 10 can be used at working pressures up to 125 psi, and the vacuum system 18 has a control capability of up to 10 mmHg. The stirrer 28 is preferably a modified frame stirrer with blades to reduce sticking of the semi-molten pasty reaction material, especially sticking to the reactor wall. The equipment should also contain a spray dryer (not shown).

Freshly prepared anhydrous potassium fluoride was used in each batch in the operation of the plant. It can be prepared in a conventional manner by first preparing a 40% w/v potassium fluoride solution, heating the solution to the boiling temperature, and pumping the solution through a dry atomizer to an operating temperature of 350-400°C, e.g. in a desiccator at 370°C. The dry powder is placed in a suitable container and used immediately. Alternatively an activated form of KF as described above, or a commercially available spray-dried KF (ground or unground) may also be used. Before starting the reaction, the reactor 10 and auxiliary operating systems should first be cleaned and dried to ensure that all systems are operable and that all raw materials are available for use. In addition the system should be checked to ensure that the bottom valve 12 is closed. If there is any doubt about the dryness of the vessel, the reactor should be heated at 105°C for 2 hours under full vacuum. After 2 hours, the container should be cooled to room temperature under vacuum, and then the vacuum should be broken by blowing nitrogen gas at room temperature, and the reaction process can be started at this time.

At the beginning of a batch operation, the reaction agitator 28 should be activated to ensure that the agitator is running smoothly. 21 kg of dry potassium fluoride powder were charged through feed port 26 into the reactor with the agitator running. 15 kg of hexachlorobenzene was then added through the feed port, followed by 0.96 kg of tetrakis(diethylamino)phosphonium bromide. Feed port 26 and valve 30 are closed. The contents of the reactor were heated to 180°C over 1 hour. Ensuring effective agitation for this particular reaction mixture is important at such rapid heating rates. The pressure in the reactor gradually increased during heating. When the material in the reactor reached 180° C., the heating controller of the reactor was adjusted to increase the temperature at a rate of 4° C. every 6 hours. The contents of the reactor were heated at this ramp rate for 42 hours (7 temperature increases totaling 28°C). Slow heating at this stage of the process is important to ensure thorough mixing of this particular reaction mixture. At this point the temperature of the reaction mixture reached approximately 208°C and the pressure inside the reactor varied hourly. The reaction was considered complete when the pressure did not change between two consecutive hourly measurements. When the pressure was constant in the range of 70-100 psi, the heating system was turned off and the reactor was cooled. At this point valve 30 is carefully opened to vent the pressure from the reactor to condenser 14 and from there into receiver 16 . Nitrogen was slowly introduced through nitrogen conduit 20 when the pressure in the reactor reached ambient atmospheric pressure. The vacuum system 18 was turned on to bring the reactor to a vacuum of 725 mmHg. Nitrogen introduced into the reactor was slowly reduced by observing the rate of distillation recovery to receiver 16 to ensure that distillation recovery was not excessive. The vacuum was gradually increased until the maximum (flat) vacuum was reached while continuously adjusting the distillation recovery rate. When the system reached room temperature, nitrogen was introduced to break the vacuum, the vacuum system was turned off, and then nitrogen was stopped. The reaction mixture product is then withdrawn from the reactor through valve 12 . The reactor was washed with boiling caustic solution, rinsed with water and dried. Follow this method to carry out 12 batches gradually. The equipment used was as previously described except that in Examples 1 and 2 a low speed frame stirrer was used. Due to the viscous nature of the reaction mixture, parts of the mixture tended to stick to the reactor walls. This problem can be alleviated by changing the mixer used for the remainder of the operation to include the use of the aforementioned knife edge frame mixer. The conditions and results of these 12 runs are shown in Table 1, where the comparative example used no catalyst. The abbreviations in the table are: HCB is hexachlorobenzene, CPFB is chloropentafluorobenzene, and DCTFB is dichlorotetrafluorobenzene.

Table 1 Example number KF adding amount kg HCB dosage kg Catalyst Added Kilograms Molar ratio, KF:HCB Response time hours HFB yield kg CPFB yield kg DCTFB yield kg HCB conversion % HFB+CPFB% molar yield 34.0 15.0 none 11.1:1 twenty four 2.5 2.5 - - 49 1 15.4 11.0 0.97 6.866:1 60 2.555 2.608 0.7353 77.64 69 2 15.4 11.0 0.98 6.866:1 82 2.4336 2.8137 0.6253 77.67 70 3 15.4 11.0 0.98 6.866:1 32 3.0964 2.9500 0.7906 90.21 81 4 21.0 15.0 1.30 6.867:1 22.5 3.7200 4.0000 1.2090 85.98 76 5 21.0 15.0 1.03 6.867:1 20 3.7011 4.2515 0.1900 78.95 78 6 21.0 15.0 1.03 6.867:1 46 4.5472 2.8490 1.8282 88.96 73 7 21.0 15.0 0.942 6.867:1 38 3.9763 4.1376 0.1900 81.09 79 8 21.0 15.0 0.96 6.867:1 44 3.9861 3.8378 0.7416 83.16 77 9 21.0 15.0 0.96 6.867:1 29.5 2.7824 4.1454 1.9082 83.86 67 10 21.0 15.0 0.96 6.867:1 34.5 3.1420 4.1447 1.7954 86.54 71 11 21.0 15.0 0.96 6.867:1 46 4.3521 4.1302 1.2931 94.41 83 12 21.0 15.0 0.96 6.867:1 46 4.4160 4.3008 1.1232 95.19 86

- Comparative example

In Table 1, the reaction time refers to the time when the reaction temperature reaches 190 ° C; the product yield is expressed in kilograms, which is obtained by analyzing the hexafluorobenzene, chloropentafluorobenzene and dichlorotetrafluorobenzene flashed from the corresponding reaction mixture. Obtained from the analysis of fluorobenzene fractions. The results of fractional distillation of the mixed products from Examples 1-12 are in good agreement with these analyses. Examples 1-12 produced 104.765 kg of mixed chlorofluorobenzenes. And the result of bulk phase fractionation gained separation and recovery is:

41.085 kg of hexafluorobenzene

43.020 kg of chloropentafluorobenzene

11.440 kg dichlorotetrafluorobenzene

Each product has a minimum purity of 99%.

It should be noted that in the above examples of the present invention, the catalytic method of the present invention is carried out at a maximum temperature of 208° C. without any auxiliary solvent or diluent. A conventional catalyst-free and solvent-free reaction of HCB with potassium fluoride involves the use of a 20-liter autoclave at a temperature of 450°C and a pressure of up to 1,500 psi using an excess of 85% KF. The batch yield of the target product based on the total starting material charged was about 12%.

Any modification of the method of the invention is possible without departing from the scope of the invention. By way of illustration and not limitation, the following modifications are possible:

(a) The catalyst or catalyst residue can be reused.

(b) When the target product is a polyfluorinated aromatic compound, the formed intermediate containing less than the target number of fluorine atoms per molecule can be reused.

(c) If the target product has a suitably high volatility, it will leave the reactor during the course of the reaction, for example substantially as soon as it is formed, thereby preventing or at least reducing overfluorination.

(d) Special processes such as azeotropic distillation drying or high-temperature spray drying can dry the alkali metal fluoride before use.

(e) The alkali metal fluoride prior to use can be dried using a multi-step drying process.

(f) Alkali metal fluorides may be reduced in particle size or colloidal at one or more stages prior to their use.

(g) The alkali metal fluoride prior to use may be treated by combining one or more drying stages with one or more particle size reduction stages.

(h) Whether or not an auxiliary solvent is used in the process, the alkali metal fluoride can be an optimized mixture consisting of a major amount of dry finely divided potassium fluoride and a small amount of dry finely divided fluorine which enhances reactivity Composition of cesium chloride.

(i) When the desired product is produced with one or more intermediates that are liquid and have a boiling point at or below the selected reaction temperature, the intermediate may act as a solvent or diluent.

(j) The ratios of selected components for any given condition can and should be optimized by careful design of pilot trials and scale-up before determining the mode of operation of a large-scale industrial plant.

(k) In addition to or as an alternative to one or more monoalkali metal fluorides such as potassium fluoride, the alkali metal reagent can be or include a more complex alkali metal salt such as a double salt, examples of which include KBF ₄ , CsBF ₄ , NaBF ₄ , K ₃ AlF ₆ , K ₂ SnF ₆ , Cs ₂ SnF ₆ , KPF _{6 , CsPF 6 ,} K ₂ SiF ₆ , Cs ₂ SiF ₆ , Na ₂ TiF ₆ , Na ₂ ZrF ₆ , K ₂ ZrF _6. Na ₂ HfF ₆ , K ₂ HfF ₆ .

(l) In addition to or as an alternative to one or more aminophosphonium catalysts of the above types, the corresponding aminoarsonium compound [(R ₂ N) ₄ As]X or amino antimony compound [(R ₂ N) ₄ Sb] X can also be used as a catalyst or cocatalyst component, wherein R and X are as previously defined.

(m) Simple quaternary ammonium salts such as tetraethylammonium bromide, tetraethylammonium chloride, tetraphenylammonium chloride, tetraethylammonium iodide, and tetraphenylammonium iodide can be used as cocatalyst groups point.

An example of this modification which constitutes a specific embodiment of the invention relates to the synthesis of chloropentafluorobenzene and/or hexafluorobenzene from hexachlorobenzene. The alkali metal fluoride component used in the process preferably comprises potassium fluoride and the aminophosphonium catalyst used is preferably at least one tetrakis(dialkylamino)phosphonium halide (especially tetrakis(diethylamino)halide) Amino)phosphonium bromide), and the stirring mixture formed by hexachlorobenzene, potassium fluoride, and aminophosphonium catalyst components is in one or more Heating is at the reaction temperature until at least most of the reaction occurs. In this particular embodiment, the agitated mixture contains solids suspended or dispersed in a continuous liquid which preferably contains a major amount (preferably 60% by volume or more at the start of the reaction) of at least A chlorofluoroperhalobenzene which is in the liquid state at least while the stirred mixture is at one or more reaction temperatures in the range of 170-240°C. Examples of such chlorofluoroperhalogenated benzenes include dichlorotetrafluorobenzene (boiling point approximately 151°C at one atmosphere), trichlorotrifluorobenzene (melting point approximately 62°C) and tetrachlorodifluorobenzene (The melting point is approximately 138°C). Among these compounds, dichlorotetrafluorobenzene is particularly desirable because it is liquid at room temperature and remains liquid at temperatures in the range of 170-240°C and moderately high pressures.

A preferred embodiment is to carry out the halogen exchange reaction according to the invention by the slurry method with at least one aprotic solvent or diluent. When the halogen exchange process is carried out by the slurry method, the reaction mixture should be anhydrous or substantially anhydrous until the temperature at which the halogen atom exchange reaction starts is reached, and preferably the reaction mixture should be anhydrous or Basically anhydrous. The term "substantially anhydrous" as used herein in relation to reaction mixtures such as mixtures of reactants, catalysts and solvents means that the total water content in the mixture is less than 2000 ppm (wt/wt) at or above 160°C for initiation of the exchange reaction And preferably less than 1500 ppm. In general, the lower the water content, the better. Excess water will kill the reaction. It is therefore necessary to use anhydrous or substantially anhydrous alkali metal fluorides (whose water content should not exceed 3000 ppm as noted above), but also to ensure that other components used are sufficiently dry (such as their water content, if any If so, it should be low enough to keep the total water content of the whole mixture below 2000ppm (wt/wt) and preferably below 1500ppm.). For example, if an industrial grade polar aprotic solvent contains excess water, the solvent needs to be dried by azeotropic distillation or molecular sieves to say 100 ppm, preferably less than 50 ppm (wt/wt) level of moisture content. Usually it is very difficult to produce, store and use chemicals under absolutely anhydrous conditions. Therefore, the term "anhydrous" as used herein is understood by those skilled in the art. If it happens that the substance used has an absolute zero water content, then it is of course anhydrous. But even if not zero water content, the substance is considered anhydrous as long as the water content is in the non-influenced trace range and the water content is within the range specified in the manufacturer's instructions and/or indicated to be anhydrous . The supplier, Aldrich Chemical Company, defines a group of listed "anhydrous solvents" as having a water content of less than 0.005% in its 1996-1997 Classification of Fine Chemicals Handbook on page 1773, which definition is not correct to the above limitations of universality. Other suppliers may specify a maximum water content for their anhydrous grades, so there is not a very clear line between anhydrous and essentially anhydrous.

The following Examples 13-21 describe the procedure for carrying out the halogen exchange process of the present invention as a slurry in an aprotic solvent. All parts given in these examples are by weight.

Example 13

The reaction equipment used was a reactor equipped with a heating device, a mechanical stirrer, feed and discharge ports, and an overhead takeover for transferring the product evaporated from the reactor to the middle part of the fractionating column . The column is equipped in sequence with a tube for collecting the top of chloropentafluorobenzene and a line for returning the condensed bottoms from the condenser to the outlet to the reactor below the liquid level. A mixture of 285 parts of hexachlorobenzene, 406 parts of anhydrous ball-milled potassium fluoride powder, 600 parts of sulfolane and 80 parts of tetrakis(diethylamino)phosphonium bromide was heated at 200°C for 40 hours while stirring Continuously transfer and fractionate volatiles. The overhead of the column is chloropentafluorobenzene, and the bottoms of the column are continuously refluxed to the reactor below the surface of the slurry.

Example 14

285 parts of hexachlorobenzene, 406 parts of anhydrous ball milled potassium fluoride powder activated by T.P.Smyth, A. Carey and B.K.Hodnett (in the citation above), 80 parts of tetrakis (diethylamino) brominated A mixture of phosphonium, 600 parts of triglyme and 80 parts of potassium fluoroborate was heated in the reactor described above at 195-200° C. for 40 hours with stirring. Volatile chloropentafluorobenzene was continuously fractionated overhead as in Example 1.

Example 15

The procedure of Example 13 was repeated in the same manner, except that 80 parts of 18-crown-6-ether was also included in the initial reaction mixture.

Example 16

The procedure of Example 13 was repeated in the same manner, except that 80 parts of cryptate 222 were also included in the initial reaction mixture.

Example 17

The procedure of Example 14 was repeated in the same manner, except that 80 parts of 18-crown-6-ether was also included in the initial reaction mixture.

Example 18

Repeat the process of Example 13 in the same manner, but also include 150 parts of pentachlorofluorobenzene, a mixture of tetrachlorodifluorobenzene and trichlorotrifluorobenzene in the initial reaction mixture (from the previous reaction recovered from the reaction mixture), and 450 parts of spray-dried potassium fluoride was added to the reactor.

Example 19

The process of Example 13 was repeated in the same manner, except that 80 parts of 18-crown-6-ether and 150 parts of dichlorotetrafluorobenzene were included in the initial reaction mixture and 450 parts of spray-dried Potassium fluoride was added to the reactor.

Example 20 below describes a preferred method for pretreating a quaternary phosphonium catalyst to remove at least a portion of impurities, particularly quaternary ammonium halides. A further description of this method is set forth in the application (Serial No. CaseOR-7060) filed concurrently with the present application and incorporated herein. The pretreated and purified catalyst was used in Examples 21 and 22, while in Example 23 the virgin untreated catalyst was used. Comparing Examples 22 and 23, which were carried out in the same manner, it can be seen that when practicing any of the embodiments of the invention there are advantages to using a pretreated and purified catalyst. Example 20

In a 1 liter flask containing 156 grams of tetrahydrofuran, add 38.9 grams of tetrakis (diethylamino) phosphonium bromide catalyst (Chordip Limited, England, 75% purity) while stirring. The slag-like insolubles (2.8 grams) It was filtered off and determined to be primarily tetraethylammonium bromide by ¹ H-NMR.The tetrakis(diethylamino]phosphonium bromide catalyst was then precipitated by adding 245 grams of anhydrous ether to the catalyst in tetrahydrofuran. The solid catalyst was filtered and dried under full vacuum for 1 hour at 50° C. Analysis of the purified catalyst (29.8 g) by ³¹ P-NMR found it to be at least 95% pure.

Example 21

To a 1 liter stainless steel stirred pressure reactor was added 12 g of the purified catalyst obtained from Example 20 dissolved in 421 g of benzonitrile (Aldrich, <50 ppm water), 164 g of spray-dried potassium fluoride (Hashimoto Chemical Corporation, Japan, 0.87 m ² /g) and 115 g of hexachlorobenzene. The top of the reactor was equipped with a 1/2 inch OD column filled with 15 inches long Pro-Pak packing, an air cooled partial condenser (also known as a lock-type rotary condenser), an air cooled Total condenser and product receiver with back pressure control valve. The reaction mixture slurry was heated and maintained at a temperature of 218-220°C for 5 hours while maintaining the pressure of the system at 14 psig and the distillation temperature of the column at 140°C. The distilled perhalogenated benzenes, mainly chloropentafluorobenzene and some hexafluorobenzene, are distilled to the top of the reactor as soon as they are formed where they are condensed and recovered. Simultaneously, other condensed perhalobenzenes are returned to the reaction mixture through the lock rotary condenser. At the end of the 5-hour reaction, the heating was stopped and the volatile products remaining in the reactor were distilled by continuously increasing the vacuum of the system to recover all the volatile products formed in the reaction. The entire distillation mixture was analyzed by gas chromatography. Based on hexachlorobenzene, the yields were 2.5% for hexafluorobenzene, 58.6% for monochloropentafluorobenzene, 23.8% for dichlorotetrafluorobenzene and 7.5% for trichlorotrifluorobenzene.

Example 22

Into a 1 liter stainless steel stirred pressure reactor was charged 12 grams of purified tetrakis(diethylamino]phosphonium chloride catalyst obtained from Example 20 dissolved in 420 grams of benzonitrile (Aldrich, <50 ppm water). Then 164 grams of spray-dried potassium fluoride (HashimotoChemical Corporation, Japan, 0.87 m ² /g) and 115 grams of hexachlorobenzene were added to the reactor. The reaction mixture was reacted at 220° C. for 5.5 hours. Then stop Heating and distilling by simply continuously increasing the vacuum of the system to transfer all volatile products formed in the reaction. The distillation mixture is analyzed by gas chromatography. The yield based on hexachlorobenzene is hexafluorobenzene 24.4%, 39.9% of monochloropentafluorobenzene, 21.9% of dichlorotetrafluorobenzene and 8.1% of trichlorotrifluorobenzene.

Example 23

Into a 1 liter stainless steel stirred pressure reactor was charged 15.1 g of purified tetrakis(diethylamino]phosphonium chloride catalyst (Chordip Limited, 75% purity). Then 164 grams of spray-dried potassium fluoride (Hashimoto Chemical Corporation, Japan, 0.87m ² /g) and 115 grams of hexachlorobenzene are added to the reactor. The reaction mixture is 220 DEG C of reaction 6.5 hours. Then stop heating and distill by simply constantly increasing the vacuum degree of this system to transfer all volatile products formed in the reaction. Analyze this distillation mixture with gas chromatography. Take hexachlorobenzene as The benchmark yields were 34.7% for hexafluorobenzene, 37.7% for monochloropentafluorobenzene, 12.3% for dichlorotetrafluorobenzene and 3.9% for trichlorotrifluorobenzene.

The presently most efficient means of performing halogen exchange to produce perhalobenzenes with at least three, preferably at least four, and more preferably at least five or six fluorine atoms in the ring is a process comprising will contain (i) at least one _finely divided alkali metal fluoride having an atomic number of 19 or higher, (ii) a perhalogenated benzene of the formula _{C6FnX6 -n} , where n is 0-4, Each X is independently a chlorine or bromine atom, (iii) a tetrakis(dihydrocarbylamino)phosphonium halide, most preferably tetrakis(diethylamino)chloride or phosphonium bromide, and (iv) at least one Polar aprotic solvent free of halogen atoms, preferably benzonitrile and/or alkyl-substituted benzonitrile in liquid state at a temperature at least as low as 20°C, and/or slurry of nitrobenzene components Perhalogenated benzenes with at least three, preferably at least four, and more preferably at least five or six fluorine atoms per molecule are formed under heated conditions. The most efficient way to produce perhalobenzenes with at least five or six fluorine atoms in the ring is a process involving:

a) heating the above-mentioned slurry formed from the above-mentioned components containing (i)-(iv) at one or more reaction temperatures at which the gas phase formed contains at least one species having at least 5 Perhalogenated benzenes with fluorine atoms; and

b) continuously transferring gas phase components from the slurry;

c) separating perhalogenated benzenes having at least 5 fluorine atoms in the ring from gas phase components; and

d) refluxing all or at least part of the gaseous phase component residues, if any, back into the slurry.

In a preferred embodiment, steps c) and d) are performed continuously so that the reaction zone is in a steady state. It is also preferred that the slurry has an initial water weight of less than 1500 ppm prior to heating the slurry to the selected reaction temperature. The slurry preferably contains 5-8 moles of said alkali metal fluoride and 0.05-0.3 moles of said catalyst per mole of perhalobenzene used to form the slurry. When the process is used to produce chloropentafluorobenzene as the main product, the preferred starting material is hexachlorobenzene, and the reaction conditions in the reaction zone are maintained such that when the reacting slurry is at a selected temperature (most preferably not above 250°C), the amount of chloropentafluorobenzene in the liquid phase of the slurry, if any, does not exceed 5% on average, based on the total weight of the liquid in the slurry. The gas phase in this case usually consists of distilled polar aprotic solvents, hexafluorobenzene, chloropentafluorobenzene, dichlorotetrafluorobenzene and trichlorotrifluorobenzene, and most preferably in the gas phase Among the perhalogenated benzenes, chloropentafluorobenzene exists in the largest amount.

Due to the discovery of the surprising effectiveness of aminophosphonium catalysts in halogen exchange reactions, the present invention allows the production of important industrial end-uses with greater efficiency and lower cost than most, if not all, existing halogen exchange technologies. product. Preparation of Pentafluorophenyl Organometallic Compounds

Pentafluorophenyl organometallic compounds are efficiently prepared by a method comprising the following steps, the method comprising: (A) preparing perhalogenated benzene with 5 fluorine atoms on the ring by the halogen exchange method of the present invention , preferably a chloropentafluorobenzene, and (B) react the perhalogenated benzene prepared and recovered in the method (A) with a Grignard reagent under the conditions of forming a pentafluorobenzene Grignard reagent, preferably a Grignard reagent exchange reaction. Steps (A) and (B) may be carried out consecutively in a given industrial plant, or may be carried out separately at different times, and also in different plants.

Alternatively, the perhalobenzene produced and recovered from process (A) in step (B) can be mixed with MR- The alkyl alkali metal compound is reacted under the conditions of forming a pentafluorophenyl alkali metal compound such as C ₆ F ₅ Li, C ₆ F ₅ Na or C ₆ F ₅ K, wherein M is an alkali metal such as lithium, sodium and potassium, R is an alkyl group having 4-12 carbon atoms. Due to the explosive nature of these alkali metal compounds, this method is not recommended, subject to availability.

In the Grignard exchange reaction, it is preferred to react chloropentafluorobenzene with a C ₃ -C ₂₀ hydrocarbyl magnesium halide Grignard reagent under an ether solvent and anhydrous reaction conditions. Preferred _C3 - _C20 hydrocarbyl magnesium halide Grignard reagents are those in which the halogen atom is bromine or iodine and in which the hydrocarbyl group is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or aralkyl Grignard reagents, and Grignard reagents having 2 to 10 carbon atoms are more preferred. Most preferred is isopropylmagnesium halide, especially isopropylmagnesium bromide. When the ratio is variable, it is preferable to use 1-2 moles of monochloropentafluorobenzene per mole of hydrocarbyl magnesium halide Grignard reagent. For a further description of this preferred halogen exchange process see _EP728,760A2 (published August 28, 1996) by Krzystowczyk et al.

Example 24, based in part on the halogen exchange method described in the aforementioned Krzystowczyk et al. European Patent Publication, describes a preferred procedure for carrying out this method.

Example 24

In a dry box, 31.45 g (0.155 mol) of chloropentafluorobenzene prepared in Example 21 and 64.42 g of isopropylmagnesium bromide (iPrMgBr) (0.141 mol) dissolved in a 2 molar ether solution were charged. into a Fischer-Potter reactor and heated to 60°C for 4.5 hours. Pentafluorophenylmagnesium bromide is formed. As currently known, the method for preparing the pentafluorophenyl Grignard reagent is the most economical and effective industrial production method among the disclosed methods.

When using bromopentafluorobenzene in the Grignard exchange reaction, ethylmagnesium bromide can be used as the starting Grignard reagent. However, as described by Tamborski et al. in J. Organometal. Chem., 1971, 26 , 153-156, it is desirable to use shorter reaction times when used in the above procedure.

In the present invention, for example, the perhalogenated benzene prepared and recovered by the halogen exchange method in the above-mentioned embodiment 21 and an alkyl alkali metal such as butyl lithium or ethyl sodium are mixed in anhydrous alkane or cycloalkane at -78 ° C. Medium (such as hexane or heptane) under inert gas protection to obtain the most complete reaction of the pentafluorophenyl alkali metal compound. Alternatively, the alkali metal pentafluorophenyl alkali metal can be prepared using the reaction of sodium metal with chloropentafluorobenzene or bromopentafluorobenzene in an inert hydrocarbon or ether reaction medium at -78°C compound. Any solids formed during this process can be removed by filtration or other means. While stirring the resulting reaction mixture and maintaining the mixture at -78°C, it is normal for a small amount of alkali metal to dissolve slowly into the hydrocarbon or ether solution of chloropentafluorobenzene or bromopentafluorobenzene. Preparation of Pentafluorophenylboron Compounds

The method for preparing pentafluorophenyl boron compounds comprises the following steps, which can be carried out continuously or in two or three steps at different times in a designated reaction device or at different production sites:

A) prepare perhalogenated benzene with 5 fluorine atoms on the ring by the halogen exchange method of the present invention, preferably monochloropentafluorobenzene;

B) converting the perhalogenated benzene obtained in A) into a pentafluorophenyl organometallic compound by the method described above; and

C) by reacting the pentafluorophenyl organometallic compound with boron trihalide or its etherate, preferably boron trifluoride or its etherate, the pentafluorophenyl organometallic compound obtained in B) is converted into pentafluoro Phenylboron compounds.

In carrying out the process, chloropentafluorobenzene is preferably formed in step A), the pentafluorophenylmagnesium bromide Grignard reagent is preferably formed in ether in step B), and the Grignard reagent is preferably formed in step C) by adding the Grignard The reaction of the reagent with boron trifluoride etherate in diethyl ether preferably forms tris(pentafluorophenyl)boron (also known as tris(pentafluorophenyl)boron).

Example 25 describes the synthesis of tris(pentafluorophenyl)boron from pentafluorophenylmagnesium bromide based in part on the aforementioned Krzystowczyk et al. European Application Patent Publication.

Example 25

Into a four-neck round low flask was added 131 mmoles of the diethyl ether solution of pentafluorophenylmagnesium bromide formed in Example 24 above. To this solution was added 5.84 g (41.4 mmol) of boron trifluoride diethyl ether while maintaining the temperature at 0°C. The resulting solution was warmed to room temperature and stirred for 16 hours to obtain tris(pentafluorophenyl)boron. The above method is the most economical and effective industrial method for producing tris(pentafluorophenyl)boron among the methods disclosed so far. Preparation of tetrakis(pentafluorophenyl)boron anion

The method for preparing tetrakis (pentafluorophenyl) boron anion comprises the following steps, which can be carried out in a designated production device continuously or intermittently, or carried out at different times and different production locations in two or more steps :

A) prepare perhalogenated benzene with 5 fluorine atoms on the ring by the halogen exchange method of the present invention, preferably monochloropentafluorobenzene;

B) converting the perhalogenated benzene obtained in A) into a pentafluorophenyl organometallic compound by the method described above,

C) convert the pentafluorophenyl organometallic compound obtained in B) into pentafluorophenylboron by reacting an organometallic compound with boron trihalide or its etherate, preferably the above-mentioned boron trifluoride or its etherate compound.

D) converting the pentafluorophenylboron obtained in step C) into a monocoordinated complex containing an unstable tetrakis(pentafluorophenyl)boron anion in a suitable solvent or diluent.

When carrying out the method, preferably in step C) the pentafluorophenyl Grignard reagent is used with boron trifluoride or boron trifluoride etherate at a rate of 4.1-4.5 moles of Grignard reagent per mole of boron trifluoride The ratio is mixed while maintaining the reaction temperature at 25-45°C. The product of this reaction is the ether soluble complex (C ₆ F ₅ ) ₄ BMgX. In addition, it is preferred that in step D) hydrocarbyl ammonium halide aqueous solution is slowly added to the complex ether solution formed in step C] while maintaining the reaction temperature below or equal to 5°C and stirring the mixture to dissolve the hydrocarbyl chloride or Ammonium bromide such as N,N-dimethylanilinium chloride or tributylammonium chloride and the ether solution of the complex formed in step C] are mixed together. It may be desirable to use an excess of hydrocarbyl ammonium chloride in this reaction.

Examples 26 and 27 describe the preparation of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium and tetrakis(pentafluorophenyl)boron trialkylammonium complexes, respectively, which are typical Contains an unstable tetrakis (pentafluorophenyl) boron anion and a ligand (such as methyl group) that can bond to a Group 4 transition metal to form a metallocene, which undergoes an irreversible reaction to form an ionic catalyst component cation.

Example 26

Boron trifluoride in ether (138.7 g, 0.98 mol) was added to the ether solution of pentafluorophenylmagnesium chloride (3326 g, 4.17 mol) formed in Example 24 at such a rate that the mixture reached reflux temperature. The mixture was added to reflux for 18 hours. The mixture was then cooled to -10°C and N,N-dimethylanilinium chloride (1142 g, 2.06 mol), previously formed from concentrated hydrochloric acid, water and N,N-dimethylaniline, was slowly added while Keep the temperature at 0 °C. After the addition, the mixture was stirred at -5°C-0°C for 1 hour. The two phases were then separated, the organic phase was washed with water and dried over _MgSO4 . Hexanetetrakis(pentafluorophenyl)boron N,N-dimethylanilinium was added under stirring to precipitate and it was recovered by filtration.

Example 27

Tetrakis(pentafluorophenyl)borontributylammonium was prepared by substituting 2.06 moles of tributylammonium chloride for N,N-dimethylanilinium chloride. Preparation of Active Polymerization Catalysts

A process for the preparation of an active polymerization catalyst suitable for use in the formation of homopolymers and copolymers of polymerizable mono-olefins, di-olefins and alkyne monomers, the process comprising the following steps, either continuously or intermittently Two or more steps are carried out separately at one production site or at two or more different production sites at different times:

A) prepare perhalogenated benzene with 5 fluorine atoms on the ring by the halogen exchange method of the present invention, preferably a chloropentafluorobenzene,

B) the perhalogenated benzene obtained in A) is converted into a pentafluorophenyl organometallic compound by the above-mentioned method,

C) by reacting the organometallic compound with boron trihalide or its etherate, preferably the above-mentioned boron trifluoride or its etherate, the pentafluorophenyl organometallic compound obtained in B) is converted into a pentafluorophenyl boron compound .

D) converting the pentafluorophenylboron obtained in step C) into a monocoordinated complex in a suitable solvent or diluent, wherein the complex contains unstable tetrakis(pentafluorophenyl) as described above ) boron anion.

E) An active catalyst is formed by a process comprising dissolving (i) a cyclopentadienyl metal compound containing a Group 4 transition metal and (ii) at least A second component containing said complex is mixed under conditions and for a period of time such that the cation of said complex is irreversible with at least one ligand of the cyclopentadienyl compound react and form a non-coordinating ion pair between the pentafluorophenyl anion and the cation generated from the cyclopentadienyl metal compound.

In the process according to the invention, it is preferred that the mixture formed in step H) above also comprises at least one other component which is (C) at least one organometallic adduct of formula R ₃ M, wherein Each R is independently a hydrocarbon group or an alkoxy group, provided that at least one R is a hydrocarbon group, and M is an aluminum or boron atom; or (D) a catalyst carrier; or (E), (C) Combination with (D). More preferably, said other component is an inorganic oxide in particulate form.

The following examples further describe the preparation of active catalysts and the use of such catalysts in the polymerization of unsaturated monomers to form useful polymers. Examples 28-50 are based in part on the examples in US Patent 5,198,140 and Examples 51-56 are based in part on US Patent 5,153,157.

Example 28

Into a 1-liter stainless steel autoclave with dry nitrogen protection, add 400 ml of dry deoxygenated hexane and 15 mg of bis(cyclopentadienyl)dimethylhafnium dissolved in 30 ml of toluene, and then add 12 mg of A solution of bis(cyclopentadienyl)dimethylhafnium in 50 ml of toluene and 30 mg of tri(n-butyl)ammonium tetrakis(pentafluorophenyl)boron formed in Example 27 above. The autoclave was pressurized with 90 psig of ethylene and stirred at 60°C for 1 hour. The autoclave was vented and opened and the polyethylene formed was recovered.

Example 29

To the autoclave of Example 15, previously vented with dry nitrogen, 400 ml of dry deoxygenated hexane and 9 mg of bis(tert-butylcyclopentadienyl)zirconium dimethyl dissolved in 25 ml of toluene and the 2.9 mg of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium solution formed in Example 26, and then 100 ml of 1-butene was added, and the autoclave was pressurized with 65 psig of ethylene and heated at 50 °C and stirred for 1 hour. The ethylene-1-butene copolymer formed in the process was recovered by venting the autoclave, cooling and drying the contents.

Example 30

Into a 1-liter stainless steel autoclave with a dry nitrogen blanket was added 400 ml of dry deoxygenated hexane and a solution of 15 mg of bis(cyclopentadienyl)dimethylhafnium dissolved in 25 ml of toluene, followed by addition of a solution containing 17 mg of di (Cyclopentadienyl)dimethylhafnium in 50 ml of toluene and 42 mg of tetrakis(pentafluorophenyl)borontri(n-butyl)ammonium formed in Example 27 above. An additional 200 mL of propylene was added and the autoclave was pressurized with 50 psig of ethylene and stirred at 60°C for 15 minutes. The autoclave was vented and opened, and the hexane remaining in the reactants was removed by distilling off under a stream of air to recover the formed copolymer of ethylene and propylene.

Examples 31-38

The procedure of Examples 28-30 was used to prepare a series of catalyst compositions and to carry out all polymerizations according to the invention. Table 1 lists the starting materials used to carry out the corresponding polymerizations. In performing each of the examples listed in Table 2, the anion source can be tetrakis(pentafluorophenyl)borontributylammonium (BAPFB) prepared in the above-mentioned Example 27 and can be the same as in the above-mentioned Example 26. Preparation of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium (MAPFB). The Group IV metallocene and anion source were dissolved in an appropriate amount of toluene and added to each example reactant.

Table 2 Example Group IV filtered metal compounds (mg) Anion source (mg) auxiliary diluent temperature time monomer 31 (Cp) ₂ Hf(Me) ₂ (36) MAPFB(11) ^no- 50℃ 15 minutes Propylene (400mL), Ethylene (120psig) 32 (Cp) ₂ Hf(Me) ₂ (12) BAPFB(30) n-Hexane 50℃ 60 minutes 1-butene (50mL), ethylene (65psig) 33 (Cp) ₂ Hf(Me) ₂ (19) BAPFB(15) n-Hexane 50℃ 45 minutes 1-butene (50mL), propylene (25mL), ethylene (60psig) 34 (Cp) ₂ Hf(Me) ₂ (72) MAPFB(16) n-Hexane 50℃ 10 minutes 1,4-Hexadiene (100mL), Propylene (50mL), Ethylene (90psig) 35 (Cp) ₂ Hf(Me) ₂ (27) BAPFB(30) n-Hexane 50℃ 60 minutes 1-Hexene (100mL), Ethylene (65psig) 36 (Cp) ₂ Hf(Me) ₂ (72) MAPFB(22) n-Hexane 40℃ 65 minutes Propylene (200mL) 37 (Cp) ₂ Hf(Me) ₂ (77) MAPFB(22) ^no- 40℃ 90 minutes Propylene (400mL) 38 rac-(Me) ₂ (SiH)(In) ₂ Hf(Me) ₂ MAPFB(5) ^no- 40℃ 270 minutes Propylene (500mL)

^-Propylene bulk polymerization Example 39

To a polymerization vessel was added 0.22 g of tetrakis(pentafluorophenyl)borontributylammonium (prepared as in Example 27 above) dissolved in 50 ml of toluene, followed by 0.1 g of bis(pentamethylcyclopentadiene base) dimethyl zirconium. The vessel was covered with a rubber septum and stirred at room temperature for 10 minutes. The vessel was then pressurized to 1.5 atmospheres with ethylene and stirred vigorously. After 15 minutes the reaction vessel was depressurized and methanol was added to destroy the catalyst. Linear polyethylene is recovered from the resulting mixture.

Example 40

Repeat the steps of Example 39, the changes made are: use 0.34 grams of the anion source prepared in the above-mentioned Example 27, and the Group 4 metallocene used is 0.13 grams of (cyclopentadienyl) (pentamethylcyclopentadiene alkenyl)zirconium dimethyl, quenched with methanol after 10 minutes. Polyethylene is produced.

Example 41

Polyethylene was prepared by following the procedure of Example 39 with the changes that 0.18 grams of the same anion source prepared in Example 27 above was used, and that the Group 4 metallocene used was 0.12 grams of bis[1,3-bis( Trimethylsilyl)cyclopentadienyl]zirconium dimethyl, quenched with methanol after 10 minutes.

Example 42

The procedure of Example 39 was repeated, except that 0.34 g of the anion source prepared in Example 27 above and 0.1 g of bis(cyclopentadienyl)zirconium dimethyl was used, and the reaction was terminated with methanol after 10 minutes. The polyethylene produced in the polymerization is recovered.

Example 43

Into a polymerization vessel were charged 0.12 g of tetrakis(pentafluorophenyl)borontributylammonium (prepared as in Example 27 above) and 0.04 g of bis(cyclopentadienyl)dimethyl in 100 ml of toluene. zirconium. The vessel was covered with a rubber septum and stirred at 60°C for 3 minutes. Then 3 ml of 1-hexene and 1.5 atmospheres of ethylene were added to the vessel. After 20 minutes the reaction vessel was depressurized and methanol was added to destroy the catalyst. An ethylene-hexene copolymer is recovered from the resulting mixture. Example 44

By mixing 550 mg of bis(trimethylsilylcyclopentadienyl) hafnium dimethyl with 800 mg of tetrakis(pentafluorophenyl) boron N,N-di An active catalyst according to the invention was prepared by reacting methylanilinium (prepared as in Example 26 above). When ethylene is passed through the solution, an exothermic reaction occurs to form polyethylene.

Examples 45-50

Six active catalysts were prepared according to the invention by mixing the following components in toluene:

Test 45: 40 mg of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium (prepared as in Example 26 above) and 17 mg of 1-bis(cyclopentadienyl)zirconium-3-bis Methylsilacyclobutane.

Test 46: 80 mg of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium (prepared as in Example 26 above) and 36 mg of 1-bis(cyclopentadienyl)titanium-3-di Methylsilacyclobutadiene.

Test 47: 85 mg tetrakis(pentafluorophenyl)borontributylammonium (prepared as in Example 27 above) and 34 mg bis(cyclopentadienyl)zirconium-2,3-dimethyl 1,3 - Butadiene.

Test 48: 39 mg of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium (prepared as in Example 26 above) and 20 mg of 1-bis(cyclopentadienyl)hafnium-3-bis Methylsilacyclobutane

Test 49: 41 mg tetrakis(pentafluorophenyl)borontributylammonium (prepared as in Example 27 above) and 21 mg bis(cyclopentadienyl)hafnium-2,3-dimethyl 1,3 - Butadiene.

Test 50: 75 mg tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium (prepared as in Example 26 above) and 53 mg (pentamethylcyclopentadienyl) (tetramethylcyclopentadienyl) pentadienylmethylene)benzyl hafnium.

Polyethylene was produced by passing ethylene into each of the six corresponding catalyst solutions.

Example 51

To an autoclave containing a dry nitrogen atmosphere was added a toluene solution (20 mL) containing 0.2 mmol of triethylboron, followed by 5 mL of toluene, 3 mg of bis(cyclopentadienyl)zirconium dimethyl and 1.5 mg of A solution of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium prepared in Example 26 above. The vessel was pressurized with 90 psi of ethylene and stirred at 40°C for 1 hour. The vessel was vented and opened, and the linear polyethylene was recovered from the autoclave.

Example 52

The operation of Example 51 was repeated, except that the toluene solution used was prepared from 5 milliliters of toluene, 4 milligrams of bis(cyclopentadienyl) dimethyl hafnium and 1.5 milligrams of tetrakis(pentafluorobenzene) prepared in the above-mentioned Example 26 base) boron N,N-dimethylanilinium formation. A linear polyethylene is produced.

Example 53

The operation of Example 51 was repeated, except that a solution formed by 20 ml of toluene and 0.2 mmol of triethylaluminum was added to the autoclave, and then a solution of 10 ml of toluene, 3 mg of bis(cyclopentadienyl) di A solution formed of methyl zirconium and 3 mg of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium prepared in Example 26 above. A linear polyethylene is produced.

Example 54

The operation of Example 51 was repeated, except that after adding the toluene solution of triethylaluminum, a compound consisting of 20 ml of toluene, 3 mg of bis(cyclopentadienyl) dimethyl hafnium and 6 mg of the above-mentioned example was used. 26 A solution formed of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium. A linear polyethylene is produced.

Example 55

Add 0.2 ml of 35% by weight triethylaluminum solution dissolved in hexane to a 1-liter stainless steel autoclave containing a dry nitrogen atmosphere, then add 10 ml of 10 ml of toluene, 36 mg of bis(cyclopentadiene base) hafnium dimethyl and 11 mg tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium prepared in Example 26 above. Propylene (400 mL) was charged to the autoclave, and the contents were heated to 40°C. The vessel was pressurized with 200 psi of ethylene and stirred at 40°C for 0.5 hours. The vessel was vented and opened, and the copolymer of ethylene and propylene was recovered from the autoclave.

Example 56

The procedure of Example 43 was repeated, except that triethylaluminum was replaced with 0.2 mmoles of triethylboron, and then the solution used was composed of 10 milliliters of toluene, 24 milligrams of bis(cyclopentadienyl) dimethyl hafnium and A solution formed by 8 mg of tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium prepared in Example 26 above. The product is an ethylene-propylene copolymer.

Examples 57-71

Supported catalyst compositions were prepared and used as polymerization catalysts by carrying out the procedures detailed in Example 15 of PCT Published Application WO91/09882A ₁ (published July 11, 1991), but in each case Both tetrakis(pentafluorophenyl)boron N,N-dimethylanilinium prepared in Example 26 above were used. The specific catalyst consumption was greatly reduced without loss of operating efficiency in each instance.

Another method for preparing a supported catalyst comprises: the pentafluorophenyl boron compound prepared according to the above-mentioned method of the present invention, preferably the tris(pentafluorophenyl) base boron prepared in this way, is mixed with a The hydroxyl groups of the metal/non-metal oxide support are reacted to form a support-bonded anion activator, which is then contacted with a suitable metallocene of a Group 4 transition metal such that the The activator protonates the metallocene, resulting in a supported ionic catalyst system comprising a transition metal cation and a support-bound anion. The support should contain surface hydroxyl groups with a pK _a value equal to or lower than that of amorphous silica, ie a pK _a value _of 11 or less. Silica-alumina meeting this criteria are the preferred support materials. Reference should be made to PCT Published Patent Application WO 96/04319A1, published February 15, 1996, for complete details of the relevant procedures and materials used in the preparation of such supported catalysts. Examples 72-92 describe this method.

Examples 72-92

Supported catalyst compositions were prepared and used as polymerization catalysts by carrying out the procedures detailed in Examples 1-21 of PCT Published Application WO96/04319A1 (published February 15, 1996), but in each case Tris(pentafluorophenyl)boron was used in forming the catalysts, and the tris(pentafluorophenyl)boron used was prepared according to the method in Example 25 above. The specific catalyst consumption was greatly reduced without loss of operating efficiency in each instance.

Another class of catalysts that can be used with high efficiency and low consumption in the present invention are catalysts prepared by a method comprising the following sequential steps, which can be carried out continuously or intermittently in a designated production unit, or in two or multiple steps are performed separately at different times and at different production locations:

A) prepare perhalogenated benzene with 5 fluorine atoms on the ring by the halogen exchange method of the present invention, preferably monochloropentafluorobenzene;

B) converting the perhalogenated benzene obtained in A) into a pentafluorophenyl organometallic compound by the method described above,

C) convert the pentafluorophenyl organometallic compound obtained in B) into pentafluorophenylboron by reacting an organometallic compound with boron trihalide or its etherate, preferably the above-mentioned boron trifluoride or its etherate compound.

D) The said pentafluorophenyl boron compound obtained from C) is contacted with a metallocene with a molecular formula of LMX ₂ under certain conditions, wherein L is a metal active site with a constrained geometric configuration and contains 50 Derivatives of delocalized π-bonded groups other than hydrogen atoms, where M is a Group 4 metal and each X is independently a hydride or a hydrocarbyl or silyl group having up to 20 carbon, silicon or germanium atoms or germyl groups to form a catalyst having a defined charge separation structure of the formula LMX ^ XA ^ , where A is the anion formed from said pentafluorophenylboron compound.

Of the pentafluorophenylboron compounds suitable for use in the present method, tris(pentafluorophenyl)boron is the most preferred reagent. As a very detailed description of the preparation and use of the catalyst, examples of suitable metallocenes of the formula _LMX can be found in EP520,732A1 published on December 30, 1992 and in USP 5 published on July 21, 1992 by JCS Stevens, 132,380.

Examples 93-207 further describe the preparation of active catalysts of the formula LMX ^ XA ^ and the use of these catalysts in the polymerization of unsaturated monomers to form useful polymeric materials.

Example 93-207

Catalyst compositions were prepared and used as polymerization catalysts by the method detailed in the first 115 examples of EP520,732A1 (published 30 December 1992), but in each case using tris(pentafluoro Substituting phenyl) boron, the tris (pentafluorophenyl) boron used is prepared according to the method of the above-mentioned embodiment 25. The specific catalyst consumption was greatly reduced without loss of operating efficiency in each instance.

It should be understood that any component expressed by a chemical name or formula anywhere in the specification and claims, whether in the singular or in the plural, is to be used in conjunction with the chemical name or chemical type (e.g., another reaction Substance, a solvent, or a diluent) is defined as the state that exists before contact with other substances. Regardless of whether any preliminary changes, transformations and/or reactions have occurred in the resulting mixture or solution or reaction medium, because such changes, transformations and/or reactions are in the specific reactants and/or components The natural result when combined under the conditions disclosed. Reactants and other materials are thus defined as components that are brought together in connection with carrying out a desired chemical reaction or forming a mixture for carrying out a desired reaction. Therefore, even if the present tense ("comprising", or "is") may be used in the claims to define a substance, ingredient and/or component, what is cited is not in accordance with the specification just in the context of it and one or more other Substance or component as it exists when it is first contacted, blended or mixed. The fact that a substance or component loses its original definition through a chemical reaction or transformation or formation of a complex during these contacting, blending or mixing processes or assumes the formation of some other chemical form, and therefore should be fully and accurately understood and identified specification and claims. The use of chemical names or molecular formulas to define components excludes the possibility that one component will be transformed into one or more conversion intermediates to enter or participate in the reaction during the reaction and change. Simply stated, there is no representation or inference that the named components must participate in the reaction in their original chemical composition, structure or form.

The present invention allows for variations thereof to be considered in practical implementation. The foregoing description is therefore not intended to, nor should it be construed, to limit the invention to this particular example. In addition, how the invention covers its protection scope will be determined by the claims and the law.

It is to be understood that the numerical ranges given in the specification can be inferred that reasonable variations can be made.

Claims (71)

1. halogen exchange method, this method comprises a kind of mixture that contains following component of heating under temperature of reaction at least: (i) at least a alkaline metal fluoride cpd in small, broken bits, (ii) on an aromatic ring, contain at least a halogenated aromatic compound of at least one ordination number greater than 9 halogen atom, (iii) a kind of An Ji Phosphonium catalyzer makes that at least one said halogen atom of said halogenated aromatic compound is replaced by fluorine atom under this temperature of reaction.

2. contain at least a four (the amino) Phosphonium of dialkyl halogenide according to the An Ji Phosphonium catalyst component that the process of claim 1 wherein.

3. be at least a four (dialkyl amido) Phosphonium muriate and/or bromides according to the An Ji Phosphonium catalyst component that the process of claim 1 wherein.

4. four (dialkyl amido) Phosphonium muriate or bromide, alkyl wherein can be identical or different, and each alkyl has the carbon atom below 12 for one or more according to the An Ji Phosphonium catalyst component that the process of claim 1 wherein.

5. be four (diethylamino) phosphonium bromides according to the An Ji Phosphonium catalyst component that the process of claim 1 wherein.

6. be four (diethylamino) phosphonium chlorides according to the An Ji Phosphonium catalyst component that the process of claim 1 wherein.

7. according to any one the method among the claim 1-6, component wherein (i) is a kind of alkaline metal fluoride cpd, and alkali-metal ordination number wherein is more than 19 or 19.

8. according to any one the method among the claim 1-6, component wherein (i) mainly is or Potassium monofluoride just.

9. according to any one the method among the claim 1-6, wherein said mixture was a kind of mixture based on solid phase before heating at least.

10. according to any one the method among the claim 1-6, wherein said mixture is at least during at least one temperature in being heated to said temperature of reaction, mainly be a kind of solid mixture that is dispersed in the continuous liquid phase, this liquid phase contains at least a not halogen-containing, polar, anhydrous or substantially anhydrous aprotic solvent.

11. according to any one the method among the claim 1-6, wherein component (ii) has a halogenated aromatic compound component that does not contain any active function groups on the aromatic ring of ordination number greater than 9 said halogen atom at least a at bonding.

12. according to any one the method among the claim 1-6, component wherein (i) mainly is or Potassium monofluoride just; And wherein said mixture is at least during at least one temperature in being heated to said temperature of reaction, mainly be a kind of solid mixture that is dispersed in the continuous liquid phase, this liquid phase contains at least a not halogen-containing, polar, anhydrous or substantially anhydrous aprotic solvent.

13. according to any one the method among the claim 1-6, component wherein (i) mainly is or Potassium monofluoride just; And wherein component (ii) has a halogenated aromatic compound component that does not contain any active function groups on the aromatic ring of ordination number greater than 9 said halogen atom at least a at bonding.

14. according to any one the method among the claim 1-6, wherein component (ii) has a halogenated aromatic compound component that does not contain any active function groups on the aromatic ring of ordination number greater than 9 said halogen atom at least a at bonding; And wherein said mixture is at least during at least one temperature in being heated to said temperature of reaction, mainly be a kind of solid mixture that is dispersed in the continuous liquid phase, this liquid phase contains at least a not halogen-containing, polar, anhydrous or substantially anhydrous aprotic solvent.

15. according to any one the method among the claim 1-6, component wherein (i) mainly is or Potassium monofluoride just; Component wherein (ii) has a halogenated aromatic compound component that does not contain any active function groups on the aromatic ring of ordination number greater than 9 said halogen atom at least a at bonding; And wherein said mixture is at least during at least one temperature in being heated to said temperature of reaction, mainly be a kind of solid mixture that is dispersed in the continuous liquid phase, this liquid phase contains at least a not halogen-containing, polar, anhydrous or substantially anhydrous aprotic solvent.

16. according to any one the method among the claim 1-6, component wherein is C at least a molecular formula (ii) ₆Cl _nBr _mF _pThe perhalogeno aromatic substance, wherein n is 0-6, m is 0-6, p is 0-5, and n, m and p add up to 6.

17. according to any one the method among the claim 1-6, component wherein is C at least a molecular formula (ii) ₆Cl _nF _pThe perhalogeno aromatic substance, wherein n is 1-6, p is 0-5, and n and p add up to 6.

18. according to any one the method among the claim 1-6, component wherein (ii) comprises hexachlorobenzene, dichloro-tetrafluoro at least for benzene or trichlorine trifluoro-benzene, perhaps wherein any two kinds any combination, perhaps all combinations of three kinds.

19. according to any one the method among the claim 1-6, component wherein (ii) is a hexachlorobenzene.

20. according to any one the method among the claim 1-6, component wherein (i) mainly is or Potassium monofluoride just; Component wherein is C at least a molecular formula (ii) ₆Cl _nBr _mF _pThe perhalogeno aromatic substance, wherein n is 0-6, m is 0-6, p is 0-5, and n, m and p add up to 6; And wherein said mixture is at least during at least one temperature in being heated to said temperature of reaction, mainly be a kind of solid mixture that is dispersed in the continuous liquid phase, this liquid phase contains at least a not halogen-containing, polar, anhydrous or substantially anhydrous aprotic solvent.

21. method according to claim 20, wherein said aprotic solvent mainly is or is (a) phenyl cyanide fully, (b) the alkyl phenyl cyanogen of at least a liquid state, (c) oil of mirbane, (d) the alkyl mononitro-benzene of at least a liquid state, or (e) be at least two kinds mixture among (a) and (b), (c), (d).

22. according to the method for claim 20, wherein form a kind of gas phase mixture of perhalogeno benzene, so that at least a more high-volatile perhalogeno benzene component is separated with one or more perhalogeno benzene components than low volatility of said gas phase mixture and is reclaimed; And said one or more are turned back in currently or later the halogen exchange reaction than the circulation of at least a portion of the perhalogeno benzene component of low volatility.

23. method according to claim 22, wherein said aprotic solvent mainly is or is (a) phenyl cyanide fully, (b) the alkyl phenyl cyanogen of at least a liquid state, (c) oil of mirbane, (d) the alkyl mononitro-benzene of at least a liquid state, or (e) be at least two kinds mixture among (a) and (b), (c), (d).

24. according to any one the method among the claim 1-6, component wherein (i) mainly is or Potassium monofluoride just; Component wherein is C at least a molecular formula (ii) ₆Cl _nF _pThe perhalogeno aromatic substance, wherein n is 1-6, p is 0-5, and n and p add up to 6; And wherein said mixture is at least during at least one temperature in being heated to said temperature of reaction, mainly be a kind of solid mixture that is dispersed in the continuous liquid phase, this liquid phase contains at least a not halogen-containing, polar, anhydrous or substantially anhydrous aprotic solvent.

25. method according to claim 24, wherein said aprotic solvent mainly is or is (a) phenyl cyanide fully, (b) the alkyl phenyl cyanogen of at least a liquid state, (c) oil of mirbane, (d) the alkyl mononitro-benzene of at least a liquid state, or (e) be at least two kinds mixture among (a) and (b), (c), (d).

26. according to the method for claim 24, wherein form a kind of gas phase mixture of perhalogeno benzene, so that at least a more high-volatile perhalogeno benzene component is separated with one or more perhalogeno benzene components than low volatility of said gas phase mixture and is reclaimed; And said one or more are turned back in currently or later the halogen exchange reaction than the circulation of at least a portion of the perhalogeno benzene component of low volatility.

27. method according to claim 26, wherein said aprotic solvent mainly is or is (a) phenyl cyanide fully, (b) the alkyl phenyl cyanogen of at least a liquid state, (c) oil of mirbane, (d) the alkyl mononitro-benzene of at least a liquid state, or (e) be at least two kinds mixture among (a) and (b), (c), (d).

28. according to any one the method among the claim 1-6, wherein

A) component (i) mainly is or is Potassium monofluoride;

B) component is C at least a molecular formula (ii) ₆Cl _nBr _mF _pThe perhalogeno aromatic substance, wherein n is 0-6, m is 0-6, p is 0-5, and n, m and p add up to 6;

C) said mixture mainly is a kind of solid mixture that is dispersed or suspended in the continuous liquid phase, and this liquid phase contains at least a not halogen-containing, polar, anhydrous or substantially anhydrous aprotic solvent;

D) said mixture is heated under temperature of reaction at least, is forming a kind of gas phase that has the perhalogeno benzene of at least 5 fluorine atoms on ring that contains under this temperature;

E) from reaction mixture, tell gas phase continuously;

F) from gas phase, be recovered in the perhalogeno benzene that ring has at least 5 fluorine atoms; And

G) with the residual component in all or this gas phase of at least a portion, if residual component is arranged, circulation turns back in dispersion or the slurry.

29. according to the method for claim 28, wherein F) and G) carry out continuously so that in conversion zone, there is the condition of stable state.

30. according to the method for claim 28, wherein component is (ii) not chloride.

31. according to the method for claim 30, wherein component (ii) contains hexabromobenzene.

32. according to the method for claim 28, wherein component is (ii) not brominated.

33. according to the method for claim 32, wherein component (ii) contains hexachlorobenzene.

34. according to the method for claim 28, dispersion or the slurry water-content before reaching temperature of reaction wherein is if there is water, by weight for being lower than 1500ppm.

35. method according to claim 28, wherein said aprotic solvent mainly is or is (a) phenyl cyanide fully, (b) the alkyl phenyl cyanogen of at least a liquid state, (c) oil of mirbane, (d) the alkyl mononitro-benzene of at least a liquid state, or (e) be at least two kinds mixture among (a) and (b), (c), (d).

36. according to the method for claim 28, wherein relative every mole of used in forming dispersion or slurry perhalogeno benzene uses said alkaline metal fluoride cpd of 5-8 mole and the said catalyzer of 0.05-0.3 mole to form dispersion or slurry.

37. method according to claim 28, reaction conditions wherein is, when described reaction slurry is in said one or more temperature of reaction following time, the amount of a chlorine phenyl-pentafluoride in the liquid phase of slurry, if any, gross weight with liquid in dispersion or the slurry is a benchmark, and average out to is not more than 5 weight %.

38. according to the method for claim 28, wherein temperature of reaction is not for being higher than 250 ℃; Wherein component is (ii) not brominated; Gas phase wherein is made up of for benzene and trichlorine trifluoro-benzene polar proton inert solvent, phenyl-hexafluoride, a chlorine phenyl-pentafluoride, the dichloro-tetrafluoro of gasification basically.

39. according to the method for claim 38, wherein used reaction conditions is that a chlorine phenyl-pentafluoride exists with maximum in the perhalogeno benzene in the gas phase.

40. according to the method for claim 38, wherein used reaction conditions is that at least 50 weight % are a chlorine phenyl-pentafluoride in all perhalogeno benzene that make in the gas phase.

41. method according to claim 28, wherein said aprotic solvent mainly is or is (a) phenyl cyanide fully, (b) the alkyl phenyl cyanogen of at least a liquid state, (c) oil of mirbane, (d) the alkyl mononitro-benzene of at least a liquid state, or (e) be at least two kinds mixture among (a) and (b), (c), (d); And dispersion or the slurry water-content before reaching temperature of reaction wherein is if there is water, by weight for being lower than 1500ppm.

42. according to the method for claim 41, wherein component is (ii) not brominated.

43. according to the method for claim 41, wherein component (ii) is a perchloro benzene.

44. according to the method for claim 43, wherein F) and G) carry out continuously so that in conversion zone, there is the condition of stable state.

45. according to the method for claim 44, wherein relative every mole of used in forming dispersion or slurry perhalogeno benzene uses said alkaline metal fluoride cpd of 5-8 mole and the said catalyzer of 0.05-0.3 mole to form dispersion or slurry; Reaction conditions wherein is, when described reaction slurry is in said one or more temperature of reaction following time, the amount of a chlorine phenyl-pentafluoride in the liquid phase of slurry if any, is a benchmark with the gross weight of liquid in dispersion or the slurry, and average out to is not more than 5 weight %.

46. method according to claim 45, wherein in all or part of gas phase thing that turns back to the condensation in the reaction mixture, its at least 80 weight % is made up of for the trichlorine trifluoro-benzene of benzene and liquefaction the dichloro-tetrafluoro of the polar proton inert solvent of liquefaction, solvent, liquefaction.

47. a method, this method comprise (A) a kind of mixture that contains following component of heating under temperature of reaction at least: (i) at least a ordination number in small, broken bits is the alkali-metal fluorochemical more than 19 or 19, and (ii) at least a molecular formula is C ₆F _nX _6-nPerhalogeno benzene, wherein n is 0-4, each X is a chlorine atom or a bromine atoms and (iii) a kind of An Ji Phosphonium catalyzer independently, makes under this temperature of reaction to form a chlorine phenyl-pentafluoride or monobromo phenyl-pentafluoride; (B) reclaim (A) formed chlorine phenyl-pentafluoride or monobromo phenyl-pentafluoride; And (C) will be converted into a kind of phenyl-pentafluoride base Ge Shi (Grignard) reagent or a kind of five alkali fluoride metallic compounds from a chlorine phenyl-pentafluoride or the monobromo phenyl-pentafluoride that (B) obtains.

48. method according to claim 47, this method comprises that also (D) by with phenyl-pentafluoride base Grignard reagent or phenyl-pentafluoride base alkali metal compound and a kind of boron trihalides or the reaction of its etherate, will be converted into phenyl-pentafluoride base boron compound from phenyl-pentafluoride base Grignard reagent or the phenyl-pentafluoride base alkali metal compound that (C) obtains.

49. according to the method for claim 48, this method comprises that also (E) will be converted into a kind of single co-ordination complex that contains unsettled four (phenyl-pentafluoride base) boron anion from the phenyl-pentafluoride base boron compound that (D) obtains a kind of suitable solvent or thinner.

50. according to the method for claim 48, this method comprises that also said phenyl-pentafluoride base boron compound and a kind of molecular formula that (E) will obtain from (D) are LMX ₂Metallocene contact, wherein L is a kind of derivative that has constraint geometric configuration metal active position and contain the delocalized pi-bond group of 50 following non-hydrogen atoms, M is a kind of metal of the 4th family, each X is independently for hydride or a kind of alkyl, silylation or germane base group with 20 following carbon, silicon or germanium atoms, and a kind of to have molecular formula be LMX to form XA The catalyzer of qualification charge separation structure, wherein A is the negatively charged ion that forms from said phenyl-pentafluoride base boron compound.

51., wherein in step (C), will be converted into a kind of phenyl-pentafluoride base Grignard reagent from a chlorine phenyl-pentafluoride or the monobromo phenyl-pentafluoride that (B) obtains according to the method for claim 47.

52. according to the method for claim 51, this method comprises that also (D) by with phenyl-pentafluoride base Grignard reagent and a kind of boron trihalides or the reaction of its etherate, will be converted into three (phenyl-pentafluoride base) borine from the phenyl-pentafluoride base Grignard reagent that (C) obtains.

53. according to the method for claim 52, this method comprises that also (E) will be converted into a kind of single co-ordination complex that contains unsettled four (phenyl-pentafluoride base) boron anion from three (phenyl-pentafluoride base) borine that (D) obtains a kind of suitable solvent or thinner.

54. according to the method for claim 52, this method comprises that also three (phenyl-pentafluoride base) borines and a kind of molecular formula that (E) will obtain from (D) are LMX ₂Metallocene contact, wherein L is a kind of derivative that has constraint geometric configuration metal active position and contain the delocalized pi-bond group of 50 following non-hydrogen atoms, M is a kind of metal of the 4th family, each X is independently for hydride or a kind of alkyl, silylation or germane base group with 20 following carbon, silicon or germanium atoms, and a kind of to have molecular formula be LMX to form XA The catalyzer of qualification charge separation structure, wherein A is the negatively charged ion that forms from said phenyl-pentafluoride base boron compound.

55. a method, this method comprises:

A) heat a kind of slurry that contains following component at least under temperature of reaction: (i) at least a ordination number in small, broken bits is the alkali-metal fluorochemical more than 19 or 19, and (ii) a kind of molecular formula is C ₆F _nX _6-nPerhalogeno benzene, wherein n is 0-4, each X is a chlorine atom or a bromine atoms independently, (iii) a kind of four (the amino) Phosphonium of dialkyl halide catalysts, (iv) at least a not halogen-containing, polar aprotic solvent makes to form a kind of gas phase that has the perhalogeno benzene of at least 5 fluorine atoms on ring that contains under this temperature;

B) from this slurry, tell gas phase continuously;

C) from this gas phase, separate and reclaim a chlorine phenyl-pentafluoride or monobromo phenyl-pentafluoride;

D) with the residual component in all or this gas phase of at least a portion, if residual component is arranged, circulation turns back in the slurry; And

E) with C) in separate and reclaim the chlorine phenyl-pentafluoride or the monobromo phenyl-pentafluoride that obtain and be converted into a kind of phenyl-pentafluoride base Grignard reagent or a kind of five alkali fluoride metallic compounds.

56. according to the method for claim 55, wherein C) in separate and reclaim the chlorine phenyl-pentafluoride that obtains or monobromo phenyl-pentafluoride at E) in be converted into a kind of phenyl-pentafluoride base Grignard reagent by the Ge Shi permutoid reaction of in a kind of ether reaction medium, carrying out.

57. according to the method for claim 55, this method also comprises

F) by with phenyl-pentafluoride base Grignard reagent or phenyl-pentafluoride base alkali metal compound and a kind of boron trihalides or the reaction of its etherate, said phenyl-pentafluoride base Grignard reagent or phenyl-pentafluoride base alkali metal compound are converted into phenyl-pentafluoride base boron compound.

58. according to the method for claim 56, this method also comprises

F) by phenyl-pentafluoride base Grignard reagent and boron trifluoride or its etherate are reacted, said phenyl-pentafluoride base Grignard reagent is converted into three (phenyl-pentafluoride base) borine in a kind of ether reaction medium.

59. according to the method for claim 57, this method also comprises

G) the said phenyl-pentafluoride base of at least a portion boron compound is converted into a kind of single co-ordination complex that contains unsettled four (phenyl-pentafluoride base) boron anion in a kind of suitable solvent or thinner.

60. according to the method for claim 58, this method also comprises

G) at least a portion said three (phenyl-pentafluoride base) borine is converted into a kind of single co-ordination complex that contains unsettled four (phenyl-pentafluoride base) boron anion in a kind of suitable solvent or thinner.

61. according to the method for claim 60, wherein said complex compound is to may be dissolved in four in said solvent or the thinner (phenyl-pentafluoride base) boron hydrocarbyl ammonium complex compound.

62. according to the method for claim 60, wherein said complex compound is four (phenyl-pentafluoride base) boron trialkyl ammonium complex compound or four (phenyl-pentafluoride base) boron N, N-dimethyl puratized agricultural spray.

63. according to any one the method among the claim 59-62, this method also comprises

H) form a kind of active catalyzer by a kind of process, this process be included in a kind of suitable solvent or the thinner (A) contained the cyclopentadienyl-containing metal compound of the 4th group 4 transition metal and (B) at least a second component that contains said complex compound mix for some time under certain conditions, said condition and time should make the positively charged ion of said complex compound and at least a part of cyclopentadienyl compounds irreversibly react, and make phenyl-pentafluoride base negatively charged ion and the positively charged ion that produces from the cyclopentadienyl-containing metal compound form a kind of non-coordinate ion pair.

64. according to the method for claim 63, step H wherein) mixture that forms also comprises at least a other component, and this other component is R for (C) at least a molecular formula ₃The organo-metallic adducts of M, wherein each R is a kind of alkyl or a kind of alkoxyl group independently, and its precondition is that at least one R is an alkyl, and M is aluminium or boron atom; Perhaps (D) a kind of support of the catalyst; Perhaps (E), combination (C) and (D).

65. according to the method for claim 64, wherein said other component is at least a tri alkyl aluminum compound or at least a trialkyl boron compound.

66. according to the method for claim 64, wherein said other component is a kind of inorganic oxide of particle form.

67. according to the method for claim 66, wherein said inorganic oxide is silicon oxide, aluminum oxide or silica-alumina.

68. according to the method for claim 57, this method also comprises

G) with the said phenyl-pentafluoride base boron compound of at least a portion under certain conditions with a kind of hydroxyl reaction of metal oxide carrier to form a kind of carrier-bound anion active agent, then the metallocene of said carrier-bound anion active agent with a kind of suitable the 4th group 4 transition metal contacted, make protonated this metallocene of this activator, thereby obtain containing a kind of transition-metal cation and a kind of carrier in conjunction with anionic loading type ionic catalyst system.

69. according to the method for claim 58, this method also comprises

G) with the basic borine of said three (phenyl-pentafluorides) of at least a portion under certain conditions with the hydroxyl reaction of a kind of silicon oxide or silica-alumina carrier to form a kind of carrier-bound anion active agent, then the metallocene of said carrier-bound anion active agent with a kind of suitable the 4th group 4 transition metal contacted, make protonated this metallocene of this activator, thereby obtain containing a kind of transition-metal cation and a kind of carrier in conjunction with anionic loading type ionic catalyst system.

70. according to the method for claim 57, this method also comprises

G) be LMX with said phenyl-pentafluoride base boron compound and a kind of molecular formula ₂Metallocene contact, wherein L is a kind of derivative that has constraint geometric configuration metal active position and contain the delocalized pi-bond group of 50 following non-hydrogen atoms, M is a kind of metal of the 4th family, each X is independently for hydride or a kind of alkyl, silylation or germane base group with 20 following carbon, silicon or germanium atoms, and a kind of to have molecular formula be LMX to form XA The catalyzer of qualification charge separation structure, wherein A is the negatively charged ion that forms from said phenyl-pentafluoride base boron compound.

71. according to the method for claim 58, this method also comprises

G) be LMX with said three (phenyl-pentafluoride base) borines and a kind of molecular formula ₂Metallocene contact, wherein L is a kind of derivative that has constraint geometric configuration metal active position and contain the delocalized pi-bond group of 50 following non-hydrogen atoms, M is a kind of metal of the 4th family, each X is independently for hydride or a kind of alkyl, silylation or germane base group with 20 following carbon, silicon or germanium atoms, and a kind of to have molecular formula be LMX to form XA The catalyzer of qualification charge separation structure, wherein A is the negatively charged ion that forms from described three (phenyl-pentafluoride base) borine.